Fluid hydroforming operation



Oct. 26, 1954 w A, REX' 2,692,847

FLUID HYDROFORMING OPERATION Filed Dec. 26, 1951 5&1

Zf/cLLterAEex oveotow l Patentedl Oct. 26, 1954 FLUID HYDROFORMING OPERATION Walter A. Rex, Westfield, N. J., assigner to standard Oil Development Company, a, corporation of Delaware Application December 26, 1951, Serial N o. 263,453

4 Claims.

This invention relates to the catalytic conversion of hydrocarbon fractions boiling Within the motor fuel boiling range of low knock rating into high octane number motor fuels rich in aromatics and particularly to a process whereby such a conversion is effected by the iiuidized solids technique.

Hydroforming is a Well known and Widely used process for treating hydrocarbon fractions boiling within the motor fuel or naphtha range to upgrade the same or increase the aromaticity and improve the anti-knock characteristics of said hydrocarbon fractions. By hydroforming is ordinarily meant an operation conducted at elevated temperatures and pressures in the presence of solid catalyst particles and hydrogen whereby the hydrocarbon fraction is increased in aromaticity and in which operation there is no net consumption of hydrogen. Hydroforming operations are ordinarily carried out in the presence of hydrogen or a hydrogen-rich recycle gas at temperatures of '750-1150 F. in the pressure range of about 50-1000 lbs. per sq. inch and in contact with such catalysts as molybdenum oxide, chromium oxide or, in general, oxides or suldes of metals of groups IV, V, VI, VII and VIII `of the periodic system of elements, alone, or generally supported on a base or spacing agent such as alumina gel, precipitated alumina, or zinc aluminate spinel. A good hydroforming catalyst is one containing about wt. per cent molybdenum oxide upon an aluminum oxide base prepared by heat treating a hydrated aluminum oxide or upon zinc aluminate spinel.

It has been proposed in application Serial No. 188,236, led October 3, 1950, to effect the hydroforming of naphtha fractions in a fluidized solids reactor system in which naphtha vapors are passed continuously through a dense fluidized bed of hydroforming catalyst particles in a reaction zone, spent catalyst particles are Withdrawn from the dense bed in the reaction zone and passed to a separate regeneration zone where` inactivating carbonaceous deposits are removed by combustion whereupon the regenerated catalyst particles are returned to the main reactorr vessel or hydroforming reaction zone. Fluid hy-` droforming as thus conducted has several fundamental advantages over fixed bed hydroforming such as 1) the operations are continuous, (2) the vessels and equipment can be designed for single rather than dual functions, (3) the reactor temperature is substantially constant throughout the reactor bed and (4) the regeneration or reconditioning of the catalyst may be readily controlled.

A particular advantage of the foregoing uid solids operation has been the fact that the freshly regenerated catalyst can be utilized to carry part ofthe heat required for the hydroforming reaction from the regeneration zone into the reaction zone. It has been proposed in this connection to discharge hot, freshly regenerated catalyst particles from the regenerator standpipe into a stream of hot, hydrogen-rich recycle gas in a transfer line whereby the catalyst particles are subjected to a reconditioning treatment involving at least a partial reduction of higher catalytic metal oxides formed during regeneration to a lower or more catalytically active form of catalytic metal oxide during its passage through the transfer line into the reaction zone. In view 0f the high temperature of the regenerated catalyst 10501200 F.) and the exothermic character of the reaction between the hot, freshly regenerated catalyst and the hydrogen, it is necessary to make the transfer line of` small diameter and short in length in order to keep the time of contact of the catalyst and hydrogen-containing gas sufficiently short to avoid overtreatment and/or thermal degradation of the catalyst. It has also been proposed to cool the freshly regenerated catalyst by direct or indirect heat transfer with recycle reactor catalyst in order to achieve better control of the pretreatment while still utilizing the sensible heat carried by the regenerated catalyst on the reactor side of the system.

It is the object of this invention to provide the art with a novel method of operating a iiuidized solids hydroforming system. l

It is also an object of this invention to provide the art with a method of operating a fluidized solids hydroforming system which avoids the necessity for subjecting the freshly regenerated hydroforming catalyst to any treatment with hydrogen or hydrogen-rich gas prior to the introduction of the freshly regenerated catalyst into the hydroforming reaction zone,

These and other objects will appear more clearly from the detailed specification and claims Which follow. y

It has now been found that it is possible in fluid hydroforming operations to add the freshly regenerated catalyst directly to the hydroforming reaction zone without treatment with hydrogen or hydrogen-rich gas even Where essentially complete removal of carbon from the catalyst is achieved in the regenerator, i. e. to less than 0.2 Wt. per cent and preferably less than 0.1 wt. per

cent carbon on catalyst, provided that the catalyst to oil ratio is low (less than about 1.5) and provided that the regenerated catalyst particles are substantially free from carbon monoxide, carbon dioxide and oxygen. At low catalyst to oil ratios the amount of freshly regenerated catalyst added to the reactor fluid bed is small in comparison to the amount of equilibrium or reactor catalyst in the fluid bed. Due to the turbulent nature of the reactor iiuid bed, the sensible heat of the freshly regenerated catalyst as well as the exothermic heat of reaction between the higher catalytic metal oxides in the freshly regenerated catalyst and the hydrogen in the reaction mixture is rapidly distributed to the equilibrium or reactor catalyst, thereby avoiding overheating or thermal degradation of the catalyst. Moreover, the reaction or reduction of the freshly regenerated catalyst is relatively rapid even at reactor temperature conditions and accordingly only a small portion of the feed is passed over unreduced catalyst.

Reference is made to the accompanying drawing illustrating a schematic flow plan of a reactor-regenerator system in accordance with the present invention.

Referring to the drawing, I is a reactor vessel provided at the bottom with an inlet line I I for the introduction of hot, hydrogen-rich or recycle process gas. A perforated plate or grid I2 is arranged horizontally in the lower part of the reactor vessel in order to insure uniform distribution of the incoming gas over the entire cross section of the reactor vessel. A separate inlet line I3 is shown for the introduction of naphtha feed above the grid member I2 although the naphtha feed may, if desired, be introduced separately or along with hydrogen-rich or recycle gas below the grid i2. The reactor vessel I0 is charged with nely divided hydroforming catalyst particles and the superficial velocity of the vapors and gases passing up through the reactor is socontrolled as to form a dense, fluidized, turbulent bed of catalyst I4 having a definite level L superposed by a dilute or disperse phase I5r comprising a small amount of catalyst en trained in vaporous reaction products. The reaction products are taken overhead from reactor I0 through a cyclone separator I6 or the like for separating entrained catalyst particles. The separated catalyst particles are returned to the dense bed I4 through the dip pipe attached to the bottom of the cyclone separator. The reaction products, essentially free from catalyst particles pass from cyclone separator I6 into product outlet line I1 leading to suitable fractionating and/or storage equipment.

Catalyst particles are continuously withdrawn from the dense bed I4 through spent catalyst withdrawal conduit I8 into an external stripper vessel i9. It will be understood'that the stripper could also be arranged within the reactor vessel itself, as by arranging a Vertical conduit or cell, preferably extending above level L and provided with an orifice or port for controlling the discharge of catalyst from the dense bed into the stripper cell or conduit. A tap 20 is arranged near the bottom of the stripper for introducing a suitable stripping gas, such as steam, nitrogen, scrubbed flue gas or the like, which will serve to remove entrained or adsorbed hydrogen or hydrocarbons that would otherwise be carried to the regeneration zone and burned therein. The stripping gas and the stripped gases and vapors are withdrawn overhead from stripper I9 and passed through line 2I into the upper part of reactor IIJ in the event that substantial amounts of catalyst are entrained and recovery thereof in reactor cyclone separator II is desired or through line 22 into product outlet line I1 in the event that it is desired to have the stripping gases and/or spent catalyst that hasbeen in contact with the stripping gas by-pass the reactor. The lower end of stripper I9 is connected at 23 to conduit 24 and forms therewith a standpipe for developing sufficient fluistatic pressure to facilitate the transfer of the spent catalyst into the regenerator side of the system. A slide valve 25 or the like is provided near the base of the conduit 24 in order to control the discharge of spent catalyst into transfer line 26. Ordinarily sufficient gas is entrained with the catalyst passing vthrough conduit 24 in order to maintain it in a fluidized or freely flowing condition. If desired, however, one or more gas taps can be provided along conduit 24 to supply uidizing gas thereto.

The stripped spent catalyst is discharged from the base of the standpipe into transfer line 26 where it is picked up by a stream of regeneration gas or air supplied through line 21. The stream of air conveys the spent catalyst particles as a dilute suspension through transfer line 26 and spent catalyst riser 28 into the bottom of regenerator vessel 30. A perforated plate or distributor grid 29 is arranged near the bottom of regenerator 30 in order to insure uniform distribution of the incoming catalyst and air over the entire cross section of the regenerator. In View of the rate at which carbonaceous deposits are burned off hydroforming catalysts under elevated reaction pressures, it is advisable to use only part, preferably not more than 40%, of the air necessary for regeneration for conveying the spent catalyst through the transfer line 26 and riser 28 and to add the remainder of the air necessary for regeneration through a separate line 3| or additional lines discharging directly into the regenerator vessel.

Since at the low catalyst circulation rates preferred there is more heat releastd from burning carbonaceous deposits `from the catalyst in the regenerator than can be carried back to the reactor with the circulating catalyst, it is necessary with most feed stocks being processed to provide cooling coils 46 through which water may be circulated to make steam or feed may be pumped to obtain preheat.

The superficial velocity of the regeneration gases through vessel 30 is so controlled as to form a dense, fluidized, turbulent bed 32 of catalyst particles and gas having a definite level L which is superposed by a dilute or disperse phase 33 in the upper part of the regenerator comprising small amounts of catalyst entrained in the regeneration gases. The regeneration gases are taken overhead from the regenerator, preferably after passage through a cyclone separator 34 or the like which serves to remove most of the catalyst particles from the regeneration gases. The separated catalyst particles are returned to the dense bed 32 through the dip pipe attached to the bottom of the cyclone separator. The re` generation gases are discharged from cyclone separator 34 into outlet line 35 and through pressure control valve 36 to a waste gas stack or to suitable storage equipment in the event that it is desired to use the regeneration gases for stripA ping purposes.

The .regenerator operation is controlled by allowing a small excess of oxygen in the exit gases.

The air valve is adjusted so thatthe desired excess of oxygen is maintained thereby assuring that essentially all deposited carbon is burned olf the catalyst. This results in a carbon content of less than 0.2 wt. per cent carbon on regenerated catalyst. Complete regeneration is further evidenced by substantially complete oxidation of the catalytic metal to the hexavalent form. For example, in a uid hydroforming operation using molybdenum oxide catalyst, analysis of equilibrium reactor catalyst indicates that the molybdenum is in essentially pentavalent form, the average valence value being generally within the range of from 4.7 to 5.0, the latter figure corresponding to the valance of molybdenum in the compound M0205. In complete regeneration the molybdenum is converted essentially to the hexavalent form orto M003, analysis of the complete- 1y regenerated catalyst indicating that the average valence value of the completely regenerated catalyst is within the range of from 5.7 to 6.0.

A wall member 3'I is arranged within the regenerator and forms with the inner wall of the regenerator a stripping space or cell 38. The wall member 3l extends above the dense bed level L' and a restriction orifice or port 39 is provided to regulate the flow of regenerated catalyst into this stripper cell. The stripper could be arranged externally of the regenerator similarly to the arrangement of spent catalyst stripper I9 with respect to reactor I or the Wall member 31 could terminate at or below the dense bed level L', in which case the catalyst would overflow from the dense bed 32 into the stripper cell. A stripping gas, such as air, nitrogen or the like, is introduced into the stripper cell through inlet line 40 in order to strip off entrained or adsorbed gaseous materials. The stripped catalyst passes from the base of the stripper cell 38 into transfer line 4I where small amounts of nitrogen may be added as a purge to free the regenerated catalyst of carbon oxides and oxygen whereupon the stripped regenerated catalyst particles are discharged through slide Valve 43, the side wall of the reactor I0 directly into the dense bed I4 within the reactor. If desired, a baflie member 44 may be provided on the inner wall of the reactor IIJ below the outlet end of conduit 4I in order to deiiect upflowing gases and vapors and prevent their entrance into conduit 4I where they would interfere with the flow of catalyst and possibly react with the regenerated catalyst and from which they would eventually escape into the regenerator and be burned. The regenerated catalyst is discharged at essentially regenerator temperature from transfer line 4|. The catalyst particles in reactor dense bed I4 are in rapid, turbulent movement and the reactor dense bed constitutes an-extremely large quantity of catalyst compared to the quantity of hot, freshly regenerated catalyst added thereto. Accordingly, the stream of hot, freshly regenerated, unpretreated catalyst particles and the sensible heat carried by said particles are rapidly dispersed or dissipated in the reactor dense bed I4. Moreover, any heat generated by the reaction between the hydrogen in the reaction mixture with higher catalytic metal oxides formed in the regeneration is also dissipated rapidly throughout the bed.

The feed or charging stock to the hydroforming reactor may be a virgin naphtha, a cracked naphtha, a Fischer-Tropsch naptha, or the like. The feed stock is preheated alone or in admixture with recycle gas to reaction temperature or to the` maximum temperature possible while avoiding thermal degradation of the feed stock.

drogen is preheated to temperatures of about 11501300 F. prior to the into inlet line I I. The preheat of the recycle gas is dependent upon the heat requirements of the particular reactions, the upper temperature limit being set by the tendency of the hydrocarbon constituents to undergo thermal degradation. The recycle gas is introduced directly into the bottom of reactor vessel I0 and should be circulated through the reactor at a rate of from about 1000 to 10,000 ou. ft. per bbl. of naphtha feed. In view of the fact that compressors for the recycle gas constitute a substantial cost item in a plant of this type, it is desirable to keep the quantity of recycle gas to the minimum amount that will keep carbon formation within bounds and at the same timesuiiice to introduce the amounts of heat necessary for the reaction.

The reactor system is charged with a mass of finely divided hydroforming catalyst particles. Suitable catalyst include Group VI metal oxides, such as molybdenum oxide, chromium oxide or tungsten oxide, or mixtures thereof upon a carrier such as activated alumina, zinc aluminate spinel or the like.` Preferred catalyst contain about 5 to l5 wt. percent molybdenum oxide or from about 10 to 40 wt. percent chromium oxide upon a suitable carrier. If desired, minor amounts of stabilizers and promoters such as silica, calcium oxide, ceria or potassia can be ineluded in the catalyst. The catalyst particles are, for the most part, between 200 and 400 mesh in size or about 0-200 microns in diameter with a major proportion between 20 and 80 microns.

The hydroforming reactor vessel should be operated at temperatures between about 850 and 925 F., preferably about 900 F. and at pressures between about 50 and 500 lbs. per sq. inch. Temperatures above 900 F. result in increased carbon formation and lower selectivity to gasoline fractions while at temperatures below about 900 F. operating severity is low and would, therefore, require an excessively large reaction vessel. Ordinarily lowering reactor-pressure below 200 lbs. per sq. inch results in increased carbon formation which becomes excessive in most cases at pressures below about '75 lbs. per sq. inch in the case of certain catalysts, such as molybdenum oxide on alumina. In the case of molybdenum oxide or chromium oxide on zinc aluminate spinel catalysts, however, the optimum pressure appears to be about 50 lbs. per sq. inch. Above 200 lbs., however, catalyst selectivity to light products (C4s and lighter) increases rapidly. The regenerator is operated at temperatures of about 1050l200 F. and at substantially the same pressure as the reactor zone. The residence time of the catalyst in the reactor is of the order of from 3 4 hours and in the regenerator from 3-15 minutes.

The weight ratio of catalyst to oil introduced into the reactor should be about 0.5 to 1.5. It is preferred to operate at catalyst to oil ratios of about 1 since ratios above about 1 to 1.5 result in introduction thereof aen-2gsm' Example I Experiments were made in batch uidlabora.- toryj equipment to distinguishbetwen. the stand.- ard-QOD-F F. pretreatwith H2 for 15V minutesA and operation in which no reduction of the catalyst was obtained prior to the introduction of feed and. recycle gastey the reactor.. It iswknown; thatr reduction at high temperatures (1l-00-1200 F.) can result in over-pretreatment or over-reduction. Because of the--heat of reduction and Athe heat ofadsorption of the Water formed in the pretreatment, it is possible to raise the catalyst bed temperature significantly during the pre'- treatment or' during reduction Which-v is carried'- out simultaneously with the hydroforming cycle, and, in effect, obtain ahightemperaturey reduction. In these ba-tchy iiuid tests, the heat-formed during the reduction wasquickly dissipated' to a uid sand batch. surrounding the catalyst. bed. so that the temperature rise above the 900 F.

reaction level Was only 30 F. This temperature risepersistedfor only 2-5 minutes and. accordingly.y the reduction whether carried outpriorl to the admission of feed and recycle gas or simultaneously withy the admission of feed and recycle gas, was essentially a lov/.temperature reduction. The results of the series of tests employing nol pretreat and the standardy 15 minute. pretreat with H2 are shown below.

[No pretreat operation] Run No; CFS-L44 1* 5** Cycle 1 2 1 2 Reactor Temp., F 900 900l 900 900 W-./Hr./W 05291 0.29. 0.130 0.28. Recycle Gas.Rate C. F./B..-.. 3, 905. 3,891. 4,047 4,194 Res; O; N. Clear C-430F` 92. 6 91. 9 91. 3' 0:6' \701;.Percent'Yie1d, (15T/130 F' 7911.' 7930' 79:8 82:13: Wt. Percent Dry Gas, U3 E 11.8 12.5 11.2` 8.9 Wt. Percent Carbon. 0.5 0.6 0.3l 0.5 Vol. Percent C4 7. 1' 6. 5- 9A 7; 5

*Feed and recycle. gas shifted` to reactor simultaneously. withre.`

[ mimpretreatwith-Hz rit-,900? F. and 200.p.s..i. gl.

Run No. CFS-L43 A. A B H l H Cycle l. 2 1 1. 2

Reactor Temp. E 900 900 900 900 900 W;/H /W 0. 29l 0.129 0.29- 0. 30f 0.28 Recycle Rate C. F /B 2,900 3, 2.800 5,100, 3,400.A Res. O. N. leal' Cf430 F.. 90. 6 91.8 9054 89.4` 88.9 VoLPercent Yield C5f-430?-`E, 82A() 82.14 82.141 82:0 82; 2; Wt. Percent Dry Gas, C3 9.0 9.5 9. 2 10.2 9. 9. Wt. Percent Carbon 0:4 0.5 0:2 0:3 Vol; Percent C4 5.4 5.1 5. 8" 6.10 5.'8\

than that obtained withl a st'andardpretreat ment. On. ai yieldeoctane; basis, the` selectivityobtained?withI the different catalyst treatments appears tor. bey equivalent. The carbonA yields for the testsi without pretreatment may beslightly higher-'than those of *the pretreat runsv when" the difference in recycle gas rate isA considered. In-A deed for short cycle timesequivalent tohigh- C/-Ol -ratios it isy indicated that thel unpretrea'ted catalystsv might give appreciably higher carbonyi'eld's, but at long'- holding times in theY reactor as in continuous operation Where only avery small portion oi the catalyst would be unred-uced in the reactor at any time, the additional carbon would be negligible.

Example .2

A number: of `runs vlereiconducted-in/a" barrelperf day: fluid hydroforming plant operating at approximately 200 lbspper sq. inch' andin contact with a` catalystzcontaining' about 9.3' wt.

molybdenum oxide upon alumina. The data obtainedare summarized-Jin. the following table:

These runs. clearly show that the regeneratedv catalyst maybe recycled. to the reactor without pretreatmentor reduction With hydrogen without loss in activity andselectivity.

The foregoingv description contains a. limi-ted.

number of embodimentsl of the `present invention. It will be understood.. however, that nu merous modifications are. possible Without departing from the spirit of the present invention.

- What. is claimedis.:

1. In aprocess for. hydroforming hydrocarbonsboiling within the. motor fuel range in contact with finely divided. hydroforming. catalyst par-A ticles..consisting;essentiallyf of. a. Group VI metal-- oxide upon. a carrier in.. accordance- Withthe fluidizedV solids technique at. temperaturesy be.-

tween about850. and 925 F., atpressures-between reaction. zone, regenerating the withdrawnv cata.- lyst. particlesfby. burning carbonaoeousdeposits therefrom with an excess of air in .ai regeneration zone,Withdraw-ingaZ stream of regenerated cata.-

lyst f-romthev regenerationv zone, stripping the` regenerated` catalyst with a non-reducing strip-A pinggas--tc substantially free the regeneratedcatalyst of. carbon. oxidesandfree oxygenA and without contacting.,A the .freshly regenerated cata--4 lystz-with hydrogen-containing or other reducing gases discharging the freshly' regeneratedcata'- lystdirectly.-` into the dense fluidized-bed of cata-v lyst particles inthe reactionv zonewherebythe'. freshly regenerated catalyst particles-.are-treated' with hydrogen-containing reactant gases while ins-intimatemixturewith .the main body of. reactoncatalystiri-:thef reaction; zone: at substantially reaction zone temperature.

- 2.. Theprocessfas denedin claim.1.inrwhiohx the catalytic: metal. in the :regenerated-catalyst isi oxidized;v to: arr average. valence valuei of fronti` 3. The process as dei-med in claim 1 in which the regeneration zone is operated at temperatures of about 10501200 F. and at essentially the same pressure as the reaction zone and the catalytic metal in the regenerated catalyst is oxidized to an average valence value of from 5.7 to 6.

4. The process as dened in claim 1 in which the regeneration zone is operated at temperatures of about 10501200 F. and at essentially the same pressure as the reaction zone, and the regenerated catalyst is discharged in this highly oxidized state and substantially at regenerator temperature directly into the dense catalyst bed in the reaction zone.

References Cited in the le of this patent UNITED STATES PATENTS Number Name Date 2,410,891 Meinert et al Nov. 12, 1946 2,518,693 Jahng Aug. 15, 1950 2,656,304 Mac Pherson, Jr., et al. Oct. 20, 1943 

1. IN A PROCESS FOR HYDROFORMING HYDROCARBONS BOILING WITHIN THE MOTOR FUEL RANGE IN CONTACT WITH FINELY DIVIDED HYDROFORMING CATALYST PARTICLES CONSISTING ESSENTIALLY OF A GROUP VI METAL OXIDE UPON A CARRIER IN ACCORDANCE WITH THE FLUIDIZED SOLIDS TECHNIQUE AT TEMPERATURES BETWEEN ABOUT 850 AND 925* F., AT PRESSURES BETWEEN ABOUT 50 TO 500 LBS. PER SQ INCH AND AT CATALYST TO OIL WEIGHT RATIOS OF ABOUT 0.5 TO 1.5, THE IMPROVEMENT WHICH COMPRISES CONTINUOUSLY WITHDRAWING A STREAM OF SPENT CATALYST PARTICLES FROM A DENSE FLUIDIZED BED OF CATALYST PARTICLES IN THE REACTION ZONE, REGENERATING THE WITHDRAWN CATALYST PARTICLES BURNING CARBONACEOUS DEPOSITS THEREFROM WITH AN EXCESS OF AIR IN A REGENERATION ZONE, WITHDRAWING A STREAM OF REGENERATED CATALYST FROM THE REGENERATION ZONE, STRIPPING THE REGENERATED CATALYST WITH A NON-REDUCING STRIPPING GAS TO SUBSTANTIALLY FREE THE REGENERATED CATALYST OF CARBON OXIDES AND FREE OXYGEN AND WITHOUT CONTACTING THE FRESHLY REGENERATED CATALYST WITH HYDROGEN-CONTAINING OR OTHER REDUCING GASES DISCHARGING THE FRESHLY REGENERATED CATALYST DIRECTLY INTO THE DENSE FLUIDIZED BED OF CATALYST PARTICLES IN THE REACTION ZONE WHEREBY THE FRESHLY REGENERATED CATALYST PARTICLES ARE TREATED WITH HYDROGEN-CONTAINING REACTANT GASES WHILE IN INTIMATE MIXTURE WITH THE MAIN BODY OF REACTOR CATALYST IN THE REACTION ZONE AT SUBSTANTIALLY REACTION ZONE TEMPERATURE. 